EP3993093A1 - Matériau d'électrode positive et batterie - Google Patents

Matériau d'électrode positive et batterie Download PDF

Info

Publication number
EP3993093A1
EP3993093A1 EP20830569.8A EP20830569A EP3993093A1 EP 3993093 A1 EP3993093 A1 EP 3993093A1 EP 20830569 A EP20830569 A EP 20830569A EP 3993093 A1 EP3993093 A1 EP 3993093A1
Authority
EP
European Patent Office
Prior art keywords
positive electrode
solid electrolyte
electrode active
active material
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20830569.8A
Other languages
German (de)
English (en)
Other versions
EP3993093A4 (fr
Inventor
Izuru SASAKI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Publication of EP3993093A1 publication Critical patent/EP3993093A1/fr
Publication of EP3993093A4 publication Critical patent/EP3993093A4/fr
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a positive electrode material for batteries and to a battery.
  • a positive electrode material in an aspect of the present disclosure contains:
  • the charge and discharge efficiency of batteries is improved.
  • a positive electrode material according to a first aspect of the present disclosure contains:
  • the charge and discharge efficiency of the battery is improved.
  • the M for the positive electrode material according to the first aspect may include yttrium.
  • the X for the positive electrode material according to any one of the first to third aspects may include at least one selected from the group consisting of Br and I.
  • the percentage of the weight of the lithium carbonate to that of the positive electrode active material in the positive electrode material according to any one of the first to fourth aspects may be larger than or equal to 1.3% by weight and smaller than or equal to 4.0% by weight.
  • the ionic conductivity of the solid electrolyte is further improved.
  • the coverage of the surface of the positive electrode active material by the coating material in the positive electrode material according to any one of the first to fifth aspects may be greater than or equal to 91.1%.
  • the positive electrode active material in the positive electrode material according to any one of the first to sixth aspects may include a lithium nickel cobalt manganese oxide.
  • the energy density of the battery and the charge and discharge efficiency of the battery are further increased.
  • a battery according to an eighth aspect of the present disclosure includes:
  • the battery has improved charge and discharge efficiency by virtue of being made with the positive electrode material according to any one of the first to seventh aspects.
  • the electrolyte layer of the battery according to the eighth aspect may contain the solid electrolyte. In such a configuration, the charge and discharge efficiency of the battery is improved.
  • the electrolyte layer of the battery according to the eighth or ninth aspect may contain a halide solid electrolyte different from the solid electrolyte. In such a configuration, the power density of the battery and the charge and discharge efficiency of the battery are improved.
  • the electrolyte layer in the battery according to any one of the eighth to tenth aspects may contain a sulfide solid electrolyte. In such a configuration, the energy density of the battery is improved.
  • a positive electrode material in Embodiment 1 contains at least one positive electrode active material, a solid electrolyte, and a coating material.
  • the solid electrolyte is a material represented by composition formula (1) below. Li ⁇ M ⁇ X ⁇ ... Formula (1)
  • ⁇ , ⁇ , and ⁇ are each independently a value greater than 0.
  • M includes at least one element selected from the group consisting of non-Li metals and metalloids. M may be at least one element selected from the group consisting of non-Li metals and metalloids.
  • X includes at least one selected from the group consisting of F, CI, Br, and I.
  • X may be at least one selected from the group consisting of F, CI, Br, and I.
  • the coating material covers the surface of the positive electrode active material and contains lithium carbonate.
  • This configuration helps improve the charge and discharge efficiency of the battery.
  • PTL 1 mentions, in the context of all-solid-state secondary batteries including a solid electrolyte that is an indium-containing compound, it is desirable that the potential versus Li of the positive electrode active material be smaller than or equal to 3.9 V on average. This, according to PTL 1, ensures a product of oxidative decomposition of the solid electrolyte will form a good coating, giving the battery good charge and discharge characteristics.
  • the literature also discloses common layered transition metal oxide positive electrodes, such as LiCoO 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 , as positive electrode active materials having a potential versus Li smaller than or equal to 3.9 V on average. The publication leaves the exact mechanism of the oxidative decomposition unclear.
  • the inventors found that for batteries made with a halide solid electrolyte as a solid electrolyte, the halide solid electrolyte oxidatively decomposes during charging even if the positive electrode active material has a potential versus Li smaller than or equal to 3.9 V on average.
  • the inventors have discovered the problem that oxidative decomposition of the halide solid electrolyte during charging affects the charge and discharge efficiency of the battery. As a cause of this, the inventors have identified the oxidation of the halogen(s) in the halide solid electrolyte.
  • an oxide layer which does not conduct lithium ions well, forms between the positive electrode active material and the halide solid electrolyte.
  • the oxide layer the inventors believe, functions as a large interfacial resistance during the electrode reaction at the positive electrode. To eliminate this problem, the manufacturer needs to limit the transfer of electrons into and out of the halide solid electrolyte and prevent the formation of the oxide layer thereby.
  • the configuration according to the present disclosure has an interposed coating material between a positive electrode active material and a halide solid electrolyte.
  • the coating material can limit the transfer of electrons into and out of the halide solid electrolyte.
  • the side reaction involving the halide solid electrolyte therefore, does not occur easily, and this can improve the charge and discharge efficiency of the battery.
  • the prevention of the side reaction will prevent the formation of the oxide layer, potentially reducing the interfacial resistance during the electrode reaction.
  • PTL 2 discloses an all-solid-state lithium battery that includes a sulfide-containing lithium-ion-conducting solid electrolyte and an active material having a surface coated with a lithium-ion-conducting oxide.
  • a lithium niobate LiNbO 3
  • lithium niobate has been the most common coating material for a positive electrode active material in a positive electrode material that contains a sulfide-containing lithium-ion-conducting solid electrolyte.
  • the inventors have found that in the context of a battery containing a halide solid electrolyte in its positive electrode material, the improvement in charge and discharge efficiency is much greater with a coating material containing lithium carbonate than with a coating material containing lithium niobate. That is, the inventors have found that the coating material that produces a significant effect varies according to the type of solid electrolyte. The principle is unclear, but the inventors believe many factors play a role in a complex manner, including the voltage resistance of the coating material, the voltage resistance of the lithium-ion-conducting solid electrolyte, the reactivity between the coating material and the active material, and the reactivity between the coating material and the solid electrolyte.
  • the "metalloids” are B, Si, Ge, As, Sb, and Te.
  • the “metals” are all elements in groups 1 to 12 in the periodic table excluding hydrogen and all elements in groups 13 to 16 excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se.
  • the “metals” are the group of those elements that can become cations when they form an inorganic compound with a halide.
  • the solid electrolyte may contain Y as a metal.
  • the ionic conductivity of the solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • Me is at least one element selected from the group consisting of non-Li and non-Y metals and metalloids.
  • m is the valency of Me.
  • Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • the ionic conductivity of the solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the ionic conductivity of the solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the solid electrolyte contained in the positive electrode material herein may be referred to as "the first solid electrolyte.”
  • the resistance of the solid electrolyte to oxidative decomposition varies according to what kind(s) and percentage(s) of element(s) the anion(s) includes.
  • the solid electrolyte is prone to oxidative decomposition particularly when X includes at least one selected from the group consisting of Br and I.
  • X includes at least one selected from the group consisting of Br and I.
  • the ions of Br and I have a large radius, which means these ions would interact with the cationic component of the halide solid electrolyte only weakly.
  • electrons would be extracted from the Br or I easily, and the solid electrolyte would be prone to oxidation.
  • X includes at least one selected from the group consisting of Br and I
  • the prevention of the oxidative decomposition of the solid electrolyte by placing a coating material on the surface of the active material brings a greater advantage because the solid electrolyte is prone to oxidative decomposition in that case.
  • the first solid electrolyte may be represented by composition formula (A1) below. Li6-3dYdX6 ... Formula (A1)
  • composition formula (A1) is two or more elements selected from the group consisting of F, CI, Br, and I.
  • composition formula (A1) 0 ⁇ d ⁇ 2.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A2) below. Li 3 YX 6 ... Formula (A2)
  • composition formula (A2) is two or more elements selected from the group consisting of F, CI, Br, and I.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A3) below. Li 3-3 ⁇ Y 1+ ⁇ Cl 6 ... Formula (A3)
  • composition formula (A3) 0 ⁇ 0.15.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A4) below. Li 3-3 ⁇ Y 1+ ⁇ Br 6 ... Formula (A4)
  • composition formula (A4) 0 ⁇ 0.25.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A5) below. Li 3-3 ⁇ +a Y 1- ⁇ -a Me a Cl 6-x-y Br x I y ... Formula (A5)
  • Me includes at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • composition formula (A5) -1 ⁇ 2, 0 ⁇ a ⁇ 3, 0 ⁇ (3-3 ⁇ +a), 0 ⁇ (1+ ⁇ -a), 0 ⁇ x ⁇ 6, 0 ⁇ y ⁇ 6, and (x+y) ⁇ 6.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A6) below. Li 3-3 ⁇ Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y ... Formula (A6)
  • Me includes at least one selected from the group consisting of Al, Sc, Ga, and Bi. Me may be at least one selected from the group consisting of Al, Sc, Ga, and Bi.
  • composition formula (A6) -1 ⁇ 1, 0 ⁇ a ⁇ 2, 0 ⁇ (1+ ⁇ -a), 0 ⁇ x ⁇ 6,0 ⁇ y ⁇ 6, and (x+y) ⁇ 6.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A7) below. Li 3-3 ⁇ -a Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y ... Formula (A7)
  • Me includes at least one selected from the group consisting of Zr, Hf, and Ti. Me may be at least one selected from the group consisting of Zr, Hf, and Ti.
  • composition formula (A7) -1 ⁇ 1, 0 ⁇ a ⁇ 1.5, 0 ⁇ (3-3 ⁇ -a), 0 ⁇ (1+ ⁇ -a), 0 ⁇ x ⁇ 6, 0 ⁇ y ⁇ 6, and (x+y) ⁇ 6.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the first solid electrolyte may be represented by composition formula (A8) below. Li 3-3 ⁇ -2a Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y ... Formula (A8)
  • Me includes at least one selected from the group consisting of Ta and Nb. Me may be at least one selected from the group consisting of Ta and Nb.
  • composition formula (A8) -1 ⁇ 1, 0 ⁇ a ⁇ 1.2, 0 ⁇ (3-3 ⁇ -2a), 0 ⁇ (1+ ⁇ -a), 0 ⁇ x ⁇ 6,0 ⁇ y ⁇ 6, and (x+y) ⁇ 6.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • the ionic conductivity of the first solid electrolyte is further improved. This helps further improve the charge and discharge efficiency of the battery.
  • Examples of compounds that can be used as first solid electrolytes include Li 3 YX 6 , Li2MgX4, Li2FeX4, Li(Al,Ga,In)X 4 , and Li 3 (Al,Ga,In)X 6 .
  • the positive electrode active material includes a material having a tendency to store and release metal ions (e.g., lithium ions).
  • metal ions e.g., lithium ions
  • Examples of materials that can be used as positive electrode active materials include lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxysulfides, and transition metal oxynitrides.
  • using lithium-containing transition metal oxide(s) as positive electrode active material(s) helps reduce the production cost and increase the average discharge voltage.
  • the positive electrode active material may include a lithium nickel cobalt manganese oxide.
  • the positive electrode active material may be a lithium nickel cobalt manganese oxide.
  • the positive electrode active material may be Li(NiCoMn)O 2 .
  • the coating material contains lithium carbonate. With its low electronic conductivity and high voltage resistance, lithium carbonate can limit the transfer of electrons between the positive electrode active material and the first solid electrolyte and prevent the oxidation of the first solid electrolyte thereby.
  • the reactivity between the positive electrode active material and lithium carbonate is low, and so is the reactivity between the halide solid electrolyte in the first solid electrolyte and lithium carbonate.
  • the movement of lithium ions is smooth, or, in other words, low-resistance interfaces can be formed. As a result, the charge and discharge efficiency of the battery is further improved.
  • the coating material contains the lithium carbonate as its primary ingredient.
  • the primary ingredient is the ingredient that is the most abundant in the coating material on a weight basis.
  • the coating material may further contain inevitable impurities, the starting materials used to form the coating material, by-products, decomposition products, etc.
  • the lithium carbonate content of the coating material may be, for example, 100% of the coating material as a whole on a weight basis (100% by weight), excluding inevitable contaminants.
  • Fig. 1 is a cross-sectional diagram illustrating a schematic structure of a positive electrode material 1000 in Embodiment 1.
  • the positive electrode material 1000 in Embodiment 1 includes first solid electrolyte particles 100, positive electrode active material particles 110, and a coating layer 111.
  • the coating layer 111 is a layer that contains the coating material. That is, there is a coating layer 111 on at least part of the surface of the positive electrode active material particles 110.
  • the coating material covers the surface of the positive electrode active material particles 110. To be more exact, the coating material is in direct contact with the positive electrode active material particles 110.
  • the positive electrode active material particles 110 and the first solid electrolyte particles 100 are separated by the coating layer 111 and are not in direct contact. In other words, the positive electrode active material and the first solid electrolyte are separated by the coating material and are not in direct contact.
  • the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material particles 110 may be larger than or equal to 1.3% by weight and smaller than or equal to 4.0% by weight. A properly adjusted percentage of the weight of the positive electrode active material particles 110 to that of lithium carbonate can ensure the transfer of electrons between the positive electrode active material particles 110 and the first solid electrolyte particles 100 will be sufficiently minor.
  • An example of how to calculate the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material particles 110 is the following method.
  • Positive electrode active material particles 110 covered with the coating material are immersed in water to make the coating material dissolve.
  • the quantity of dissolved carbonate ions is determined by ion chromatography.
  • the weight of lithium carbonate is calculated from the quantity of carbonate ions. Using the weight of the positive electrode active material particles 110 employed for preparation and the calculated weight of lithium carbonate, the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material particles 110 is calculated.
  • Another method is to use ICP emission spectrometry and x-ray photoelectron spectroscopy (XPS).
  • Positive electrode active material particles 110 covered with the coating material are immersed in water to make the coating material dissolve.
  • the weight of dissolved lithium is determined by ICP emission spectrometry.
  • the percentage A of the weight of lithium in the coating material to that of the positive electrode active material particles 110 is calculated.
  • the weight of lithium includes lithium contained in the lithium carbonate and that in any other lithium salt.
  • positive electrode active material particles 110 covered with the coating material is analyzed by XPS.
  • the abundance of lithium is calculated from the Li 1s spectrum.
  • the abundance of the carbonate ion is calculated from the C 1s spectrum.
  • the abundance of lithium includes lithium contained in the lithium carbonate and that in any other lithium salt.
  • the abundance of the carbonate ion is that of lithium carbonate. From the abundance of lithium and that of the carbonate ion, the percentage B of the abundance of lithium carbonate in the coating material to that of lithium is calculated. A ⁇ B gives the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material particles 110.
  • the coverage of the surface of the positive electrode active material particles 110 by lithium carbonate can be calculated using, for example, x-ray photoelectron spectroscopy (XPS). Specifically, the C 1s spectrum and the 2p spectra of transition metals are measured. For example, if the transition metals contained in the positive electrode active material particles 110 are Ni, Co, and Mn, the C 1s, Ni 2p, Co 2p, and Mn 2p spectra are measured. Then the areas of the C 1s, Ni 2p 1/2 , Ni 2p3/2, Co 2p 1/2 , Co 2p3/2, Mn 2p 1/2 , and Mn 2p3/2 peaks are calculated.
  • XPS x-ray photoelectron spectroscopy
  • the abundance of carbon is calculated.
  • the abundance percentages of Ni (atom%), Co (atom%), and Mn (atom%) are calculated likewise.
  • the abundance of transition metals (atom%) is the sum of the abundance percentages of Ni, Co, and Mn.
  • the relative abundance of transition metals to that of carbon is determined.
  • the relative abundance of transition metals to that of carbon represents the percentage exposure of the positive electrode active material particles 110. One hundred percent minus the percentage exposure gives the coverage of the surface of the positive electrode active material by the coating material.
  • the coverage of the surface of the positive electrode active material particles 110 by the coating material may be greater than or equal to 91.1%. In such a configuration, the energy density of the battery and the charge and discharge efficiency of the battery are further increased. The coverage of the surface of the positive electrode active material particles 110 by the coating material may be smaller than or equal to 100%.
  • the coating layer 111 may cover the positive electrode active material particles 110 uniformly. This will prevent direct contact between the positive electrode active material particles 110 and the first solid electrolyte particles 100, thereby helping reduce the side reaction involving the first solid electrolyte particles 100. The charge and discharge efficiency of the battery, therefore, will be improved.
  • the coating layer 111 may cover part of the surface of the positive electrode active material particles 110. Multiple positive electrode active material particles 110 come into direct contact where they have no coating layer 111 on, improving interparticle conduction of elections between the positive electrode active material particles 110.
  • the battery therefore, can be capable of high-power operation.
  • the thickness of the coating layer 111 may be larger than or equal to 1 nm and smaller than or equal to 100 nm.
  • the thickness of the coating layer 111 is larger than or equal to 1 nm, direct contact will be prevented between the positive electrode active material particles 110 and the first solid electrolyte particles 100, which helps reduce the side reaction involving the first solid electrolyte particles 100. The charge and discharge efficiency of the battery, therefore, will be improved.
  • the thickness of the coating layer 111 is smaller than or equal to 100 nm, the thickness of the coating layer 111 is not too large. The internal resistance of the battery, therefore, is sufficiently small. As a result, the energy density of the battery is increased.
  • the thickness of the coating layer 111 may be larger than or equal to 10 nm and smaller than or equal to 40 nm.
  • the thickness of the coating layer 111 is larger than or equal to 10 nm, direct contact will be prevented between the positive electrode active material particles 110 and the first solid electrolyte particles 100 to a greater fullness, which helps reduce the side reaction involving the first solid electrolyte particles 100.
  • the charge and discharge efficiency of the battery therefore, will be improved to a greater degree of sufficiency.
  • the thickness of the coating layer 111 is smaller than or equal to 40 nm, the internal resistance of the battery is even smaller. As a result, the energy density of the battery is increased.
  • direct observation of the thickness of the coating layer 111 using a transmission electron microscope can be used to determine the thickness of the coating layer 111.
  • An example of a method for measuring the thickness of the coating layer 111 is as follows. The thickness on a certain particle is measured at any multiple points (e.g., five points), and the average is reported as "the thickness of the coating layer 111 on the certain particle.” The thickness of the coating layer is calculated on ten particles in the same way, and the average of the results is reported as "the thickness of the coating layer 111.”
  • the shape of the first solid electrolyte particles 100 in Embodiment 1 is not critical.
  • the shape of the first solid electrolyte particles 100 in Embodiment 1 may be, for example, needle-like, spherical, or ellipsoidal.
  • the shape of the first solid electrolyte particles 100 may be ball-shaped.
  • the median diameter of the first solid electrolyte particles 100 may be smaller than or equal to 100 ⁇ m.
  • the median diameter of the first solid electrolyte particles 100 is smaller than or equal to 100 ⁇ m, the positive electrode active material particles 110 and the first solid electrolyte particles 100 can form a good state of dispersion in the positive electrode material 1000. The charge and discharge characteristics of the battery, therefore, are improved.
  • the median diameter of the first solid electrolyte particles 100 may be smaller than or equal to 10 ⁇ m.
  • the positive electrode active material particles 110 and the first solid electrolyte particles 100 can form a good state of dispersion in the positive electrode material 1000.
  • the median diameter of particles is a diameter determined from the size distribution by volume measured by laser diffraction and corresponding to a cumulative volume of 50% (d50).
  • the median diameter of the first solid electrolyte particles 100 may be smaller than that of the positive electrode active material particles 110.
  • the first solid electrolyte particles 100 and the positive electrode active material particles 110 can form a better state of dispersion at the electrode.
  • the shape of the positive electrode active material particles 110 in Embodiment 1 is not critical.
  • the shape of the positive electrode active material particles 110 in Embodiment 1 may be, for example, needle-like, spherical, or ellipsoidal.
  • the shape of the positive electrode active material particles 110 may be ball-shaped.
  • the median diameter of the positive electrode active material particles 110 may be larger than or equal to 0.1 ⁇ m and smaller than or equal to 100 ⁇ m.
  • the positive electrode active material particles 110 and the first solid electrolyte particles 100 can form a good state of dispersion in the positive electrode material 1000.
  • the charge and discharge efficiency of the battery therefore, can be improved.
  • the median diameter of the positive electrode active material particles 110 is smaller than or equal to 100 ⁇ m, lithium diffusion inside the positive electrode active material particles 110 will be rapid.
  • the battery therefore, can be capable of high-power operation.
  • the first solid electrolyte particles 100 and the coating layer 111 may be in contact with each other as illustrated in Fig. 1 .
  • the positive electrode material 1000 in Embodiment 1 may include multiple collections of first solid electrolyte particles 100 and multiple collections of positive electrode active material particles 110.
  • the quantity of the first solid electrolyte particles 100 and that of the positive electrode active material particles 110 may be the same or may be different.
  • the first solid electrolyte in Embodiment 1 can be produced by, for example, the following method.
  • Raw-material powders of binary halides that will give the desired ratio of composition are prepared. For example, if Li 3 YCl 6 is produced, LiCI and YCl 3 are prepared in a molar ratio of 3:1.
  • the raw-material powders are mixed and ground well, the raw-material powders are reacted together using the method of mechanochemical milling. Alternatively, the raw-material powders may be heat-treated in a vacuum after thorough mixing and grinding.
  • the structure of the crystal phase (crystal structure) in the solid electrolyte can be determined by customizing the process and parameters for the reaction between the raw-material powders.
  • Embodiment 2 is described. What has already been described in Embodiment 1 is omitted where appropriate.
  • Fig. 2 is a cross-sectional diagram illustrating a schematic structure of a battery 2000 in Embodiment 2.
  • the battery 2000 in Embodiment 2 includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the positive electrode 201 contains a positive electrode material 1000 as in Embodiment 1 above.
  • the electrolyte layer 202 is between the positive electrode 201 and the negative electrode 203.
  • the battery has improved charge and discharge efficiency.
  • the ratio by volume "v1:100-v1" between the positive electrode active material particles 110 and the first solid electrolyte particles 100 in the positive electrode 201 may be such that 30 ⁇ v1 ⁇ 95.
  • v1 represents the percentage by volume of the positive electrode active material particles 110 assuming the total volume of the positive electrode active material particles 110 and the first solid electrolyte particles 100 in the positive electrode 201 is 100.
  • 30 ⁇ v1 the energy density of the battery can be high enough.
  • v1 ⁇ 95 the battery can be capable of high-power operation.
  • the thickness of the positive electrode 201 may be larger than or equal to 10 ⁇ m and smaller than or equal to 500 ⁇ m.
  • the thickness of the positive electrode 201 is larger than or equal to 10 ⁇ m, the energy density of the battery is high enough.
  • the thickness of the positive electrode 201 is smaller than or equal to 500 ⁇ m, the battery can be capable of high-power operation. That is, when the thickness of the positive electrode 201 is adjusted to be within an appropriate range, the battery combines sufficiently high energy density and high-power operation.
  • the electrolyte layer 202 is a layer containing an electrolyte.
  • the electrolyte is, for example, a solid electrolyte. That is, the electrolyte layer 202 may be a solid electrolyte layer.
  • the solid electrolyte contained in the electrolyte layer 202 herein may be referred to as "the second solid electrolyte.”
  • An example of a second solid electrolyte, contained in the electrolyte layer 202, is first solid electrolyte particles 100 as in Embodiment 1.
  • the electrolyte layer 202 may contain a first solid electrolyte as in Embodiment 1.
  • the second solid electrolyte, contained in the electrolyte layer 202, may be a halide solid electrolyte having a composition different from that of first solid electrolyte particles 100 as in Embodiment 1.
  • the electrolyte layer 202 may contain a halide solid electrolyte having a composition different from that of first solid electrolyte particles 100 as in Embodiment 1
  • the halide solid electrolyte contained in the electrolyte layer 202 may contain Y as a metal.
  • the halide solid electrolyte contained in the electrolyte layer 202 can be a material mentioned as that for the first solid electrolyte particles 100 in Embodiment 1.
  • the second solid electrolyte, contained in the electrolyte layer 202, may be a sulfide solid electrolyte.
  • the electrolyte layer 202 may contain a sulfide solid electrolyte.
  • the energy density of the battery is improved.
  • the battery can be made with a low-potential negative electrode material, such as graphite or metallic lithium.
  • Sulfide solid electrolytes that can be used include Li 2 S-P 2 S 5 , Li 2 S-SiS 2 , Li2SB2S3, Li2S-GeS2, Li 3.25 Ge 0.25 P 0.75 S 4 , and Li 10 GeP 2 S 12 . These may be doped, for example with LiX, Li 2 O, MO q , or Li p MO q.
  • X is at least one selected from the group consisting of F, CI, Br, and I.
  • M is at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn.
  • p and q are each independently a natural number.
  • the second solid electrolyte, contained in the electrolyte layer 202, may even be an oxide solid electrolyte, polymer solid electrolyte, or complex hydride solid electrolyte.
  • oxide solid electrolytes examples include NASICON solid electrolytes, typified by LiTi 2 (PO 4 ) 3 and its substituted derivatives, (LaLi)TiO 3 -based perovskite solid electrolytes, LISICON solid electrolytes, typified by Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 , and their substituted derivatives, garnet-based solid electrolytes, typified by Li 7 La 3 Zr 2 O 12 and its substituted derivatives, Li 3 PO 4 and its N-substituted derivatives, and glass or glass-ceramic electrolytes formed by a base Li-B-O compound, such as LiBO 2 or Li 3 BO 3 , and a dopant, such as Li 2 SO 4 or Li 2 CO 3 .
  • NASICON solid electrolytes typified by LiTi 2 (PO 4 ) 3 and its substituted derivatives
  • Examples of polymer solid electrolytes that can be used include compounds of a polymer and a lithium salt.
  • the polymer may have the ethylene oxide structure.
  • a polymer having the ethylene oxide structure helps further increase ionic conductivity as it can contain more of the lithium salt.
  • Lithium salts that can be used include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), and LiC(SO 2 CF 3 ) 3 .
  • One lithium salt selected from those listed as examples can be used alone.
  • a mixture of two or more lithium salts selected from those listed as examples can be used.
  • complex hydride solid electrolytes examples include LiBH 4 -LiI and LiBH 4 -P 2 S 5 .
  • the solid electrolyte layer may contain the second solid electrolyte as its primary ingredient. That is, the percentage of the second solid electrolyte in the solid electrolyte layer may be, for example, larger than or equal to 50% of the solid electrolyte layer as a whole on a weight basis (larger than or equal to 50% by weight).
  • the percentage of the second solid electrolyte in the solid electrolyte layer may be, for example, larger than or equal to 70% of the solid electrolyte layer as a whole on a weight basis (larger than or equal to 70% by weight).
  • the solid electrolyte layer may further contain inevitable impurities, the starting materials used to synthesize the second solid electrolyte, by-products, decomposition products, etc., while containing the second solid electrolyte as its primary ingredient.
  • the percentage of the second solid electrolyte in the solid electrolyte layer may be, for example, 100% of the solid electrolyte layer as a whole on a weight basis (100% by weight), excluding inevitable contaminants.
  • the solid electrolyte layer may be totally the second solid electrolyte.
  • the solid electrolyte layer may contain two or more of the materials listed as examples of second solid electrolytes.
  • the solid electrolyte layer may contain a halide solid electrolyte and a sulfide solid electrolyte.
  • the thickness of the electrolyte layer 202 may be larger than or equal to 1 ⁇ m and smaller than or equal to 300 ⁇ m. When the thickness of the electrolyte layer 202 is larger than or equal to 1 ⁇ m, the positive electrode 201 and the negative electrode 203 do not short-circuit easily. When the thickness of the electrolyte layer 202 is smaller than or equal to 300 ⁇ m, the battery can be capable of high-power operation.
  • the negative electrode 203 contains a material having a tendency to store and release metal ions (e.g., lithium ions).
  • the negative electrode 203 contains a negative electrode active material.
  • Examples of negative electrode active materials that can be used include metallic materials, carbon materials, oxides, nitrides, tin compounds, and silicon compounds.
  • a metallic material may be a pure metal or may be an alloy.
  • Examples of metallic materials include lithium metal and lithium alloys.
  • Examples of carbon materials include natural graphite, coke, graphitizing carbon, carbon fiber, spherical carbon, artificial graphite, and amorphous carbon. For reasons of capacity per unit area, silicon (Si), tin (Sn), silicon compounds, and tin compounds can be used.
  • the negative electrode 203 may contain a solid electrolyte.
  • the solid electrolyte may be one mentioned as an example of a material for the electrolyte layer 202.
  • the battery can be capable of high-power operation by virtue of increased conductivity to lithium ions inside the negative electrode 203.
  • the median diameter of the negative electrode active material may be larger than or equal to 0.1 ⁇ m and smaller than or equal to 100 ⁇ m.
  • the median diameter of the negative electrode active material is larger than or equal to 0.1 ⁇ m, the negative electrode active material and the solid electrolyte can form a good state of dispersion in the negative electrode. The charge and discharge characteristics of the battery, therefore, are improved.
  • the median diameter of the negative electrode active material is smaller than or equal to 100 ⁇ m, lithium diffusion inside the negative electrode active material will be rapid. The battery, therefore, can be capable of high-power operation.
  • the median diameter of the negative electrode active material may be greater than that of the solid electrolyte. This allows for the formation of a good state of dispersion between the negative electrode active material and the solid electrolyte.
  • the ratio by volume "v2:100-v2" between the negative electrode active material and the solid electrolyte in the negative electrode 203 may be such that 30 ⁇ v2 ⁇ 95.
  • v2 represents the percentage by volume of the negative electrode active material assuming the total volume of the negative electrode active material and the solid electrolyte in the negative electrode 203 is 100.
  • the energy density of the battery is high enough.
  • v2 ⁇ 95 the battery can be capable of high-power operation.
  • the thickness of the negative electrode 203 may be larger than or equal to 10 ⁇ m and smaller than or equal to 500 ⁇ m. When the thickness of the negative electrode 203 is larger than or equal to 10 ⁇ m, the energy density of the battery is high enough. When the thickness of the negative electrode 203 is smaller than or equal to 500 ⁇ m, the battery can be capable of high-power operation.
  • a binder may be contained for the purpose of improving adhesion between particles.
  • the binder is used to improve the binding of the material(s) forming the electrode.
  • binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resins, polyamides, polyimides, polyamide-imides, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyethers, polyethersulfones, hexafluoropolypropylene, styrene-butadiene rubber, and carboxymethyl cellulose.
  • Copolymers of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene can be used as binders. Mixtures of two or more selected from these may even be used.
  • At least one of the positive electrode 201 or negative electrode 203 may contain a conductive additive for the purpose of increasing electronic conductivity.
  • conductive additives include the graphite substances, such as natural graphite and artificial graphite, carbon blacks, such as acetylene black and Ketjenblack, conductive fibers, such as carbon fiber and metallic fiber, metallic powders, for example of fluorinated carbon or aluminum, conductive whiskers, for example of zinc oxide or potassium titanate, conductive metal oxides, such as titanium oxide, and conductive polymers, such as polyaniline, polypyrrole, and polythiophene.
  • a carbon-based conductive additive helps reduce the cost.
  • Examples of shapes the battery in Embodiment 2 can have include a coin, a cylinder, a square, a sheet, a button, a flat plate, and a stack of layers.
  • a coating solution was prepared by dissolving 2.3 mg of metallic lithium in 2 g of super-dehydrated ethanol (Wako Pure Chemical).
  • NCM Li(NiCoMn)O 2
  • NCM Li(NiCoMn)O 2
  • the dry powder was put into an alumina crucible and heated for 10 hours at 400°C in an oxygen atmosphere.
  • the heated powder was ground back into particles in the agate mortar.
  • the positive electrode active material of Example 1 was obtained as particles with a coating material on their surface layer.
  • the coating material was lithium carbonate.
  • the first solid electrolyte and an SEBS binder were weighed out to a ratio by weight of 1:0.022.
  • the mixture was dissolved or dispersed in p-chlorotoluene as a solvent, giving a slurry of ion-conducting material.
  • the first solid electrolyte and the positive electrode active material were weighed out to a ratio by weight of 30:70.
  • the mixture was kneaded for 6 minutes at 1600 rpm using a planetary centrifugal mixer (THINKY, ARE-310), giving positive electrode slurry.
  • the positive electrode slurry was applied to a current collector made of copper foil.
  • the positive electrode slurry was dried for 1 hour at 100°C in a vacuum to give a positive electrode plate.
  • a 9.2-mm diameter round disk was cut out of the resulting positive electrode plate by punching the hole of that size through the plate. In this way, the positive electrode of Example 1 was produced.
  • the positive electrode active material of Example 2 was obtained as particles with a coating material on their surface layer in the same way Example 1 except that the weight of the metallic lithium dissolved in super-dehydrated ethanol was changed to 5.7 mg.
  • the positive electrode of Example 2 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Example 2.
  • the positive electrode active material of Example 3 was obtained as particles with a coating material on their surface layer in the same way Example 1 except that the weight of the metallic lithium dissolved in super-dehydrated ethanol was changed to 11.5 mg.
  • the positive electrode of Example 3 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Example 3.
  • the positive electrode active material of Example 4 was obtained as particles with a coating material on their surface layer in the same way Example 1 except that the weight of the metallic lithium dissolved in super-dehydrated ethanol was changed to 22.9 mg.
  • the positive electrode of Example 4 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Example 4.
  • the positive electrode active material of Comparative Example 1 was obtained in the same way Example 1 except that the positive electrode active material was changed to untreated NCM.
  • the positive electrode of Comparative Example 1 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Comparative Example 1.
  • the positive electrode active material of Comparative Example 2 was obtained as particles with a coating material on their surface layer in the same way Example 1 except that the weight of the metallic lithium dissolved in super-dehydrated ethanol was changed to 45.8 mg.
  • the positive electrode of Comparative Example 2 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Comparative Example 2.
  • a coating solution was prepared by dissolving 5.95 g of lithium ethoxide (Kojundo Chemical) and 36.43 g of niobium pentaethoxide (Kojundo Chemical) in 500 mL of super-dehydrated ethanol (Wako Pure Chemical).
  • the formation of the coating material on NCM as the positive electrode active material was with the use of a tumbling fluidized granulating-coating machine (Powrex, FD-MP-01E).
  • the amount of positive electrode active material added was 1 kg.
  • the number of revolutions for stirring was 400 rpm.
  • the rate of solution delivery was 6.59 g/min.
  • the treated powder was put into an alumina crucible, and the crucible was removed to the ambient atmosphere.
  • the heated powder was ground back into particles in an agate mortar.
  • the positive electrode active material of Comparative Example 3 was obtained as particles with a coating material on their surface layer.
  • the coating material was lithium niobate (LiNbO 3 ).
  • the positive electrode of Comparative Example 3 was obtained in the same way as in Example 1 except that the positive electrode active material used was changed to that of Comparative Example 3.
  • the positive electrode active materials prepared in Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were immersed in water to make the coating material dissolve.
  • the quantity of dissolved carbonate ions was quantitatively analyzed by ion chromatography.
  • the weight of lithium carbonate was calculated from the quantity of carbonate ions. Using the weight of the positive electrode active material employed for preparation and the calculated weight of lithium carbonate, the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material was determined.
  • the positive electrode active materials prepared in Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were analyzed by x-ray photoelectron spectroscopy (XPS). The analysis was with the use of ULVAC-PHI's Quantera SXM. The soft x-ray source was AlK ⁇ radiation.
  • the C 1s, Ni 2p, Co 2p, and Mn 2p spectra of each of the positive electrode active materials prepared in Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were measured.
  • the areas of the C 1s, Ni 2p 1/2 , Ni 2p3/2, Co 2p 1/2 , Co 2p3/2, Mn 2p 1/2 , and Mn 2p3/2 peaks were calculated. From the relative area of the peak for C to the total area of the peaks for C, Ni, Co, and Mn, the abundance of carbon (atom%) was calculated. The abundance percentages of Ni (atom%), Co (atom%), and Mn (atom%) were calculated likewise.
  • the abundance of transition metals is the sum of the abundance percentages of Ni, Co, and Mn.
  • the relative abundance of transition metals to that of carbon which means the percentage exposure of the positive electrode active material particles 110, was determined.
  • the coverage of the surface of the positive electrode active material by the coating material was figured out by subtracting the percentage exposure from 100%. In Example 3, Example 4, and Comparative Example 2, the abundance of transition metals was below the detection limit. In Example 3, Example 4, and Comparative Example 2, therefore, the coverage of the positive electrode active material was 100%.
  • the raw-material powders were ground in a mortar to mix. Then the resulting mixture was milled at 510 rpm for 10 hours using a planetary ball mill (Fritsch, P-7), giving a vitreous solid electrolyte.
  • the vitreous solid electrolyte was heated for 2 hours at 270 degrees in an inert atmosphere. In this way, Li 2 S-P 2 S 5 was obtained as a glass-ceramic solid electrolyte.
  • the battery was placed in a thermostatic chamber at 25°C.
  • the battery was charged at a constant current that would be a C-rate of 0.05C (20-hour rate) relative to the theoretical capacity of the battery, and charging was ended at a voltage of 3.7 V.
  • the battery was discharged at a current that would be a C-rate of 0.05C, and discharging was ended at a voltage of 1.9 V.
  • the theoretical capacity of the batteries was calculated assuming that the theoretical capacity per unit weight of NCM was 200 mAh/g.
  • the initial charge and discharge efficiency is the percentage of the initial discharge capacity to the initial charge capacity.
  • the initial charge and discharge efficiency of the batteries of Example 1 to 4 was higher than that of the batteries of Comparative Examples 1 to 3.
  • a reason for this is that the batteries of Examples 1 to 4 satisfied the relation that the percentage of the weight of lithium carbonate in the coating material to that of the positive electrode active material is larger than or equal to 1.3% by weight and smaller than or equal to 4.0% by weight.
  • the lithium carbonate coverage of the surface of the positive electrode active material was greater than or equal to 91.1%.
  • the initial charge and discharge efficiency of the batteries of Example 1 to 4 was higher than that of the battery of Comparative Example 3.
  • a reason for this is that the positive electrode active material used in the batteries of Examples 1 to 4 was covered with lithium carbonate.
  • the charge and discharge efficiency of a battery is improved when the positive electrode material contains a positive electrode active material, a first solid electrolyte, and a coating material, the first solid electrolyte is represented by composition formula (1) below, Li ⁇ M ⁇ X ⁇ ... Formula (1) where ⁇ , ⁇ , and ⁇ are each independently a value greater than 0, M includes at least one element selected from the group consisting of non-Li metals and metalloids, and X includes at least one selected from the group consisting of F, CI, Br, and I, and the coating material covers the surface of the positive electrode active material and contains lithium carbonate.
  • M includes at least one element selected from the group consisting of non-Li metals and metalloids
  • X includes at least one selected from the group consisting of F, CI, Br, and I
  • the coating material covers the surface of the positive electrode active material and contains lithium carbonate.
  • the battery according to the present disclosure can be used as, for example, an all-solid-state lithium secondary battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP20830569.8A 2019-06-26 2020-04-28 Matériau d'électrode positive et batterie Pending EP3993093A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019118144 2019-06-26
PCT/JP2020/018121 WO2020261757A1 (fr) 2019-06-26 2020-04-28 Matériau d'électrode positive et batterie

Publications (2)

Publication Number Publication Date
EP3993093A1 true EP3993093A1 (fr) 2022-05-04
EP3993093A4 EP3993093A4 (fr) 2022-08-03

Family

ID=74061899

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20830569.8A Pending EP3993093A4 (fr) 2019-06-26 2020-04-28 Matériau d'électrode positive et batterie

Country Status (5)

Country Link
US (1) US20220045318A1 (fr)
EP (1) EP3993093A4 (fr)
JP (1) JPWO2020261757A1 (fr)
CN (1) CN113614948A (fr)
WO (1) WO2020261757A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111201643B (zh) * 2018-01-26 2024-05-28 松下知识产权经营株式会社 电极材料和电池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004014300A (ja) * 2002-06-06 2004-01-15 Sony Corp 非水電解質電池及びその製造方法
JP5108205B2 (ja) 2005-02-28 2012-12-26 国立大学法人静岡大学 全固体型リチウム二次電池
WO2007004590A1 (fr) 2005-07-01 2007-01-11 National Institute For Materials Science Batterie au lithium entierement a l'etat solide
JP2015072818A (ja) * 2013-10-03 2015-04-16 トヨタ自動車株式会社 被覆正極活物質およびリチウム固体電池

Also Published As

Publication number Publication date
US20220045318A1 (en) 2022-02-10
WO2020261757A1 (fr) 2020-12-30
JPWO2020261757A1 (fr) 2020-12-30
EP3993093A4 (fr) 2022-08-03
CN113614948A (zh) 2021-11-05

Similar Documents

Publication Publication Date Title
EP3745504B1 (fr) Matériau d'électrode et batterie
WO2019135322A1 (fr) Matériau d'électrode positive et batterie
WO2019146236A1 (fr) Matériau d'électrode positive et batterie
TWI568064B (zh) 複合負電極材料
EP4174022A1 (fr) Matériau d'électrode positive et batterie
EP3745503A1 (fr) Matériau d'électrode positive et batterie l'utilisant
EP3745519A1 (fr) Batterie
JP7486092B2 (ja) 正極材料、および、電池
EP4046971A1 (fr) Matériau d'électrolyte solide et batterie l'utilisant
WO2021220924A1 (fr) Matériau d'électrode positive et batterie
EP4134350A1 (fr) Matériau d'électrode positive et batterie
WO2021220927A1 (fr) Matériau d'électrode positive et batterie
EP4117071A1 (fr) Électrolyte solide, cellule électrochimique le comprenant et procédé de fabrication dudit l'électrolyte solide
US20220045318A1 (en) Positive electrode material and battery
WO2022244445A1 (fr) Substance active de cathode revêtue, matériau de cathode et batterie
CN117203794A (zh) 正极材料及电池
WO2023002827A1 (fr) Matériau d'électrode positive et batterie
US20220328804A1 (en) Electrode and battery
EP4141995A1 (fr) Batterie
CN117616600A (zh) 正极材料及电池
CN117337497A (zh) 被覆正极活性物质、正极材料及电池
CN117413394A (zh) 电池
CN117413393A (zh) 电池

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20211103

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

A4 Supplementary search report drawn up and despatched

Effective date: 20220706

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 4/02 20060101ALN20220630BHEP

Ipc: C01F 17/00 20200101ALI20220630BHEP

Ipc: H01M 10/0562 20100101ALI20220630BHEP

Ipc: H01M 10/0525 20100101ALI20220630BHEP

Ipc: H01M 4/62 20060101ALI20220630BHEP

Ipc: H01M 4/525 20100101ALI20220630BHEP

Ipc: H01M 4/505 20100101ALI20220630BHEP

Ipc: H01M 4/36 20060101ALI20220630BHEP

Ipc: H01M 4/131 20100101AFI20220630BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20240328